EP1474475B1 - Composition de caoutchouc pour pneumatique comportant un agent de couplage a fonction polythiosulfenamide - Google Patents

Composition de caoutchouc pour pneumatique comportant un agent de couplage a fonction polythiosulfenamide Download PDF

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Publication number
EP1474475B1
EP1474475B1 EP02796682A EP02796682A EP1474475B1 EP 1474475 B1 EP1474475 B1 EP 1474475B1 EP 02796682 A EP02796682 A EP 02796682A EP 02796682 A EP02796682 A EP 02796682A EP 1474475 B1 EP1474475 B1 EP 1474475B1
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Prior art keywords
tyre according
group
inorganic filler
isopropyl
formula
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EP02796682A
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German (de)
English (en)
French (fr)
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EP1474475A1 (fr
Inventor
José Carlos ARAUJO DA SILVA
Christiane Blanchard
Gérard Mignani
Salvatore Pagano
Jean-Claude Tardivat
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Michelin Recherche et Technique SA Switzerland
Michelin Recherche et Technique SA France
Societe de Technologie Michelin SAS
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Michelin Recherche et Technique SA Switzerland
Michelin Recherche et Technique SA France
Societe de Technologie Michelin SAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C15/00—Tyre beads, e.g. ply turn-up or overlap
    • B60C15/06—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0008—Compositions of the inner liner
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0025—Compositions of the sidewalls
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/548—Silicon-containing compounds containing sulfur

Definitions

  • the present invention relates to compositions of diene elastomers reinforced with a white or inorganic filler, particularly intended for the manufacture of tires or semi-finished products for tires, in particular treads of these tires.
  • binding agents for coupling reinforcing inorganic fillers and diene elastomers.
  • the filler in order to obtain the optimum reinforcing properties conferred by a filler, the filler should be present in the elastomeric matrix in a final form which is at once as finely divided as possible and distributed the most homogeneous way possible.
  • the load has a very good ability, on the one hand to incorporate into the matrix during mixing with the elastomer and to deagglomerate, on the other hand to to disperse homogeneously in this matrix.
  • Such rubber compositions comprising reinforcing inorganic fillers, for example of the silica or alumina type, have for example been described in patents or patent applications.
  • a coupling agent also called binding agent, whose function is to ensure the connection between the surface of the inorganic filler particles and the elastomer, while facilitating the dispersion of this load inorganic within the elastomeric matrix.
  • the coupling agents must not be confused with simple inorganic filler agents which, in a known manner, may comprise the active Y function with respect to the inorganic filler but lack the active X function vis-à-vis the inorganic filler. of the diene elastomer.
  • Coupling agents in particular (silica / diene elastomer), have been described in numerous documents, the best known being bifunctional organosilanes bearing three organoxysilyl functional groups (especially alkoxysilyl) as function Y, and, as function X of at least one function capable of reacting with the diene elastomer such as in particular a sulfur-containing functional group (ie, comprising sulfur).
  • polysulphide alkoxysilanes in particular TESPT
  • TESPT polysulphide alkoxysilanes
  • TESPT polysulphide alkoxysilanes
  • silica a reinforcing inorganic filler
  • they are the coupling agents most commonly used today in tire rubber compositions.
  • These coupling agents are organosilicon compounds which have the essential characteristic of carrying, as function X, a particular polythiosulfenamide functional group. They do not pose the aforementioned problems of premature roasting posed in particular by mercaptosilanes, while offering the rubber compositions high reinforcing properties combined on the one hand with excellent processability in the green state and a very good vulcanization ability .
  • the invention also relates to the use of a rubber composition according to the invention for the manufacture of tires or for the manufacture of semi-finished products intended for such tires, these semi-finished products being chosen in particular in the group constituted by the treads, the sub-layers intended for example to be placed under these treads, the crown reinforcing plies, the sidewalls, the carcass reinforcement plies, the heels, the protectors Tubes and inner tires for tubeless tire.
  • the invention also relates to these tires and these semi-finished products themselves, when they comprise an elastomeric composition according to the invention, these tires being intended to equip passenger vehicles, 4x4 vehicles (with 4 wheel drive), SUV ( “Sport Utility Vehicles” ), two wheels (including bicycles or motorcycles), such as industrial vehicles chosen from light trucks, "heavy vehicles” - ie, subway, bus, road transport equipment (trucks, tractors, trailers), off-the-road vehicles - agricultural or civil engineering machinery, aircraft, other transport or handling vehicles.
  • 4x4 vehicles with 4 wheel drive
  • SUV Sport Utility Vehicles
  • two wheels including bicycles or motorcycles
  • industrial vehicles chosen from light trucks, "heavy vehicles” - ie, subway, bus, road transport equipment (trucks, tractors, trailers), off-the-road vehicles - agricultural or civil engineering machinery, aircraft, other transport or handling vehicles.
  • the invention particularly relates to tire treads, which treads can be used in the manufacture of new tires or for retreading used tires; thanks to the compositions of the invention, these treads have both a low rolling resistance, a very good adhesion and a high resistance to wear.
  • the invention furthermore relates to the use as a coupling agent (inorganic filler / diene elastomer), in a diene elastomer composition reinforced with an inorganic filler intended for the manufacture of tires, of a compound organosilicon at least bifunctional, graftable on the elastomer by means of a sulfur group, polythiosulfenamide function, corresponding to the formula (I) above.
  • a coupling agent inorganic filler / diene elastomer
  • a compound organosilicon at least bifunctional, graftable on the elastomer by means of a sulfur group, polythiosulfenamide function, corresponding to the formula (I) above.
  • the rubber compositions are characterized before and after firing, as indicated below.
  • the Mooney plasticity measurement is carried out according to the following principle: the composition in the green state (ie, before firing) is molded in a cylindrical chamber heated to 100 ° C. After one minute of preheating, the rotor rotates within the test tube at 2 revolutions / minute and the useful torque is measured to maintain this movement after 4 minutes of rotation.
  • the measurements are carried out at 130 ° C. in accordance with the French standard NF T 43-005 (1991).
  • the evolution of the consistometric index as a function of time makes it possible to determine the toasting time of the rubber compositions, evaluated according to the above-mentioned standard by the parameter T5 (case of a large rotor), expressed in minutes, and defined as being the time required to obtain an increase in the consistometric index (expressed in MU) of 5 units above the minimum value measured for this index.
  • Traction data processing also makes it possible to plot the modulus curve as a function of elongation (see attached figure), the modulus used here being the true secant modulus measured in first elongation, calculated by reducing to the actual section of the specimen and not to the initial section as before for the nominal modules.
  • T i is the induction time, that is to say the time required for the beginning of the vulcanization reaction
  • T ⁇ (for example T 99 ) is the time necessary to reach a conversion of ⁇ %, that is to say ⁇ % (for example 99%) of the difference between the minimum (C min ) and maximum ( C max ).
  • the difference (denoted ⁇ couple expressed in dN.m) is also measured between C max and C min, which makes it possible to evaluate the vulcanization efficiency, as well as the conversion rate constant denoted K (expressed in min -1 ), d order 1, calculated between 30% and 80% conversion, which in turn allows to appreciate the kinetics of vulcanization (the higher K is, the faster the kinetics).
  • the rubber compositions according to the invention are based on at least each of the following constituents: (i) a (at least one) diene elastomer, (ii) an (at least one) inorganic filler as a reinforcing filler, ( iii) a (at least one) specific organosilicon compound as a coupling agent (inorganic filler / diene elastomer).
  • composition based on means a composition comprising the mixture and / or the reaction product in situ of the various constituents used, some of these basic constituents being capable of or intended to react. between them, at least in part, during the various phases of manufacture of the composition, especially during its vulcanization.
  • elastomer or "diene” rubber is meant in known manner an elastomer derived at least in part (i.e. a homopolymer or a copolymer) of monomers dienes (monomers bearing two carbon-carbon double bonds, conjugated or not).
  • iene elastomer is used herein to mean a diene elastomer derived at least in part from conjugated diene monomers having a level of units or units of diene origin (conjugated dienes) which is greater than 15% (%). in moles).
  • diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins of the EPDM type do not fall within the above definition and may in particular be described as "essentially saturated” diene elastomers. "(low or very low diene origin, always less than 15%).
  • the term “highly unsaturated” diene elastomer is particularly understood to mean a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%.
  • diene elastomer Although it is applicable to any type of diene elastomer, it will be understood by those skilled in the art of the tire that the present invention, particularly when the rubber composition is intended for a tire tread, is firstly put into practice. with essentially unsaturated diene elastomers, in particular of type (a) or (b) above.
  • conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di (C 1 -C 5 alkyl) -1,3-butadienes, such as, for example, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl- 1,3-butadiene, an aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene.
  • 2,3-dimethyl-1,3-butadiene 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl- 1,3-butadiene, an aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene.
  • Suitable vinyl aromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the commercial mixture "vinyl-toluene", para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene.
  • the copolymers may contain between 99% and 20% by weight of diene units and between 1% and 80% by weight of vinyl aromatic units.
  • the elastomers may have any microstructure which is a function of the polymerization conditions used, in particular the presence or absence of a modifying and / or randomizing agent and the amounts of modifying and / or randomizing agent used.
  • the elastomers can be for example block, statistical, sequenced, microsequenced, and be prepared in dispersion or in solution; they may be coupled and / or starred or functionalized with a coupling agent and / or starring or functionalization.
  • Polybutadienes and in particular those having a 1,2-unit content of between 4% and 80%, or those having a cis-1,4 content of greater than 80%, polyisoprenes and copolymers of butadiene- styrene and in particular those having a styrene content of between 5% and 50% by weight and more particularly between 20% and 40%, a 1,2-butadiene content of the butadiene part of between 4% and 65%, a trans-1,4 bond content of between 20% and 80%, butadiene-isoprene copolymers and in particular those having an isoprene content of between 5% and 90% by weight and a glass transition temperature (Tg, measured according to ASTM standard D3418-82) from -40 ° C to -80 ° C, isoprene-styrene copolymers and in particular those having a styrene content of between 5% and 50% by weight and a Tg of between -25 ° C and -5
  • butadiene-styrene-isoprene copolymers are especially suitable those having a styrene content of between 5% and 50% by weight and more particularly of between 10% and 40%, an isoprene content of between 15% and 60%.
  • the diene elastomer of the composition according to the invention is chosen from the group of highly unsaturated diene elastomers consisting of polybutadienes (BR), polyisoprenes (IR) and natural rubber (NR). , butadiene copolymers, isoprene copolymers and mixtures of these elastomers.
  • Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR) and isoprene-copolymers.
  • SBIR butadiene-styrene
  • composition according to the invention is particularly intended for a tire tread, whether it is a new or used tire (in the case of retreading).
  • the diene elastomer is for example an SBR, whether it is an emulsion-prepared SBR ("ESBR") or a solution-prepared SBR ("SSBR "), or a blend (mixture) SBR / BR, SBR / NR (or SBR / IR), or BR / NR (or BR / IR).
  • SBR emulsion-prepared SBR
  • SSBR solution-prepared SBR
  • an SBR elastomer use is made in particular of an SBR having a styrene content of between 20% and 30% by weight, a vinyl bond content of the butadiene part of between 15% and 65%, a bond content of trans-1,4 between 15% and 75% and a Tg of between -20 ° C and -55 ° C.
  • SBR copolymer preferably prepared in solution (SSBR)
  • SSBR polybutadiene
  • BR polybutadiene
  • the diene elastomer is in particular an isoprene elastomer;
  • isoprene elastomer is understood to mean, in known manner, a homopolymer or copolymer of isoprene, in other words a diene elastomer chosen from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), different isoprene copolymers and mixtures of these elastomers.
  • isoprene copolymers examples include copolymers of isobutene-isoprene (butyl rubber - IIR), isoprene-styrene (SIR), isoprene-butadiene (BIR) or isoprene-butadiene-styrene (SBIR).
  • This isoprene elastomer is preferably natural rubber or synthetic cis-1,4 polyisoprene; of these synthetic polyisoprenes, polyisoprenes having a content (mol%) of cis-1,4 bonds greater than 90%, more preferably still greater than 98%, are preferably used.
  • the diene elastomer may also consist, in whole or in part, of another highly unsaturated elastomer such as, for example, an SBR elastomer.
  • the composition in accordance with the invention may contain at least one essentially saturated diene elastomer, in particular at least one EPDM copolymer, which this copolymer is, for example, used or not mixed with one or more of the above-mentioned highly unsaturated diene elastomers.
  • compositions of the invention may contain a single diene elastomer or a mixture of several diene elastomers, the diene elastomer (s) may be used in combination with any type of synthetic elastomer other than diene, or even with polymers other than elastomers, for example thermoplastic polymers.
  • the white or inorganic filler used as reinforcing filler may constitute all or only part of the total reinforcing filler, in the latter case associated for example with carbon black.
  • the reinforcing inorganic filler constitutes the majority, ie more than 50% by weight of the total reinforcing filler, more preferably more than 80% by weight of this total reinforcing filler.
  • the reinforcing inorganic filler is a mineral filler of the silica (SiO 2 ) or alumina (Al 2 O 3 ) type, or a mixture of these two fillers.
  • the silica used may be any reinforcing silica known to those skilled in the art, in particular any precipitated or fumed silica having a BET surface and a CTAB specific surface both less than 450 m 2 / g, preferably from 30 to 400 m 2 / g.
  • Highly dispersible precipitated silicas are preferred, particularly when the invention is used for the manufacture of tires having a low rolling resistance;
  • highly dispersible silica means in a known manner any silica having a significant ability to deagglomeration and dispersion in an elastomeric matrix, observable in known manner by electron or optical microscopy, thin sections.
  • Such preferred highly dispersible silicas there may be mentioned Perkasil silica KS 430 from Akzo, silica BV3380 from Degussa, silicas Zeosil 1165 MP and 1115 MP from Rhodia, silica Hi-Sil 2000 of the PPG company, the Zeopol 8741 or 8745 silicas of the Huber Company, precipitated precipitated silicas such as for example the "doped" aluminum silicas described in the application EP-A-0 735 088 .
  • the reinforcing alumina preferably used is a highly dispersible alumina having a BET surface area ranging from 30 to 400 m 2 / g, more preferably from 60 to 250 m 2 / g, an average particle size of at most 500 nm, more preferably at most equal to 200 nm, as described in the application EP-A-0 810 258 supra.
  • aluminas "Baikalox""A125",”CR125”,”D65CR” from the company Baikowski.
  • the physical state under which the reinforcing inorganic filler is present is indifferent, whether in the form of powder, microbeads, granules, pellets, beads or any other densified form.
  • the term "reinforcing inorganic filler” also refers to mixtures of different reinforcing inorganic fillers, in particular of highly dispersible silicas and / or aluminas as described above.
  • the reinforcing inorganic filler used in particular if it is silica, preferably has a BET surface area of between 60 and 250 m 2 / g. more preferably between 80 and 200 m 2 / g.
  • the reinforcing inorganic filler can also be used in blending (mixing) with carbon black.
  • Suitable carbon blacks are all carbon blacks, especially blacks of the HAF, ISAF, SAF type conventionally used in tires and particularly in tire treads. By way of nonlimiting examples of such blacks, mention may be made of N115, N134, N234, N339, N347 and N375 blacks.
  • the amount of carbon black present in the total reinforcing filler can vary within wide limits, this amount of carbon black being preferably less than the amount of reinforcing inorganic filler present in the rubber composition.
  • compositions according to the invention in particular in the treads incorporating such compositions, it is preferable to use, in a small proportion, a carbon black in combination with the reinforcing inorganic filler, at a preferential rate of between 2 and 20%. pce, more preferably in a range of 5 to 15 phr. In the ranges indicated, it benefits from the coloring properties (black pigmentation agent) and anti-UV carbon blacks, without also penalizing the typical performance provided by the reinforcing inorganic filler, namely low hysteresis (decreased rolling resistance) and high adhesion on wet, snowy or icy ground.
  • the total reinforcing filler content is between 10 and 200 phr, more preferably between 20 and 150 phr, the optimum being different depending on the intended applications; indeed, the level of reinforcement expected on a bicycle tire, for example, is in a known manner much lower than that required on a tire capable of driving at high speed in a sustained manner, for example a motorcycle tire, a tire for a passenger vehicle or for commercial vehicles such as Heavy Trucks.
  • the amount of reinforcing inorganic filler is preferably between 30 and 140 phr, more preferably included in a range of 50 to 120 pce.
  • the BET surface area is determined in a known manner by adsorption of gas using the method of Brunauer-Emmett-Teller described in "The Journal of the American Chemical Society” Vol. 60, page 309, February 1938 , more precisely according to the French standard NF ISO 9277 of December 1996 [multipoint volumetric method (5 points) - gas: nitrogen - degassing: 1 hour at 160 ° C - relative pressure range p / po : 0.05 to 0.17].
  • the CTAB specific surface is the external surface determined according to the French standard NF T 45-007 of November 1987 (method B).
  • a coupling agent inorganic filler / diene elastomer
  • Y inorganic filler / diene elastomer
  • X a sulfur function
  • organicsilicon (or “organosilicon”) compound is to be understood, by definition, an organic compound containing at least one carbon-silicon bond.
  • the divalent group A is preferably chosen from saturated or unsaturated aliphatic hydrocarbon groups, carbocyclic, saturated, unsaturated and / or aromatic, monocyclic or polycyclic groups, and groups having a saturated or unsaturated aliphatic hydrocarbon portion and a carbocyclic portion. as defined above.
  • This group A preferably has from 1 to 18 carbon atoms, it more preferably represents an alkylene chain, a saturated cycloalkylene group, an arylene group, or a divalent group consisting of a combination of at least two of these groups. He's more preferentially chosen from C 1 -C 18 alkylenes and C 6 -C 12 arylenes; it may be substituted or interrupted by one or more heteroatoms, chosen in particular from S, O and N. According to a particularly preferred embodiment of the invention, the group A represents a C 1 -C 8 alkylene, more preferably still a C 1 -C 4 alkylene chain, especially methylene, ethylene or propylene, more preferably still propylene .
  • the number x is then an integer which is equal to 2, 3 or 4, preferably 2 or 3.
  • this number may be a fractional average number when the synthesis route gives rise to a mixture of polysulfide groups each having a different number of sulfur atoms; in such a case, the synthesized polythiosulfenamide group is in fact constituted by a distribution of polysulphides, ranging from S 2 disulphide to heavier polysulphides, centered on a mean value (in mole) of the "x" (fractional number) between 2 and 4, more preferably between 2 and 3.
  • the monovalent hydrocarbon group represented by R 1 may be aliphatic, linear or branched, or carbocyclic, in particular aromatic; it may be substituted or unsubstituted, saturated or unsaturated.
  • an aliphatic hydrocarbon group comprises in particular from 1 to 25 carbon atoms, more preferably from 1 to 12 carbon atoms.
  • alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, neopentyl, 2-methylbutyl, 1-ethylpropyl, hexyl , isohexyl, neohexyl, 1-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 1,3-dimethylbutyl, 2-ethylbutyl, 1-methyl-1-ethylpropyl, heptyl, 1-methylhexyl, 1-propylbutyl, 4,4 dimethylpentyl, octyl, 1-methylheptyl, 2-ethylhexyl, 5,5-dimethylhexyl, nonyl, decyl, 1-methylnonyl, 3,
  • the unsaturated aliphatic hydrocarbon groups that may be used comprise one or more unsaturations, preferably one, two or three unsaturations of the ethylenic (double bond) or / and acetylenic (triple bond) type.
  • unsaturations preferably one, two or three unsaturations of the ethylenic (double bond) or / and acetylenic (triple bond) type.
  • the unsaturated aliphatic hydrocarbon groups comprise a single unsaturation.
  • carbocyclic radical is meant a monocyclic or polycyclic radical, optionally substituted, preferably C 3 -C 50 .
  • it is a C 3 -C 18 radical which is preferably mono-, bi- or tricyclic.
  • the carbocyclic radical comprises more than one ring nucleus (in the case of polycyclic carbocycles), the cyclic rings are condensed in pairs. Two condensed nuclei can be ortho-condensed or peri.
  • the carbocyclic radical may comprise, unless otherwise indicated, a saturated part and / or an aromatic part and / or an unsaturated part.
  • saturated carbocyclic radicals are cycloalkyl groups.
  • the cycloalkyl groups are C 3 -C 18 , more preferably C 5 -C 10 .
  • Mention may in particular be made of cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl or norbornyl radicals.
  • the unsaturated carbocycle or any unsaturated carbocyclic moiety has one or more ethylenic unsaturation, preferably one, two or three. It advantageously comprises from 6 to 50 carbon atoms, more preferably from 6 to 20, for example from 6 to 18 carbon atoms.
  • Examples of unsaturated carbocycles are C 6 -C 10 cycloalkenyl groups.
  • Examples of aromatic carbocyclic radicals are C 6 -C 18 aryl groups and in particular phenyl, naphthyl, anthryl and phenanthryl.
  • a group having both a hydrocarbon aliphatic moiety and a carbocyclic moiety as defined above is, for example, an arylalkyl group such as benzyl, or an alkylaryl group such as tolyl.
  • substituents of the hydrocarbon aliphatic groups or moieties and carbocyclic groups or moieties are, for example, alkoxyl groups in which the alkyl moiety is preferentially as defined above.
  • R 1 preferably comprises from 1 to 25 carbon atoms.
  • R 1 is selected from the group consisting of hydrogen, alkyl, linear or branched C 1 -C 8 cycloalkyl, C 5 -C 10 aryl C 6 - C 18 and (C 6 -C 18 ) aryl- (C 1 -C 8 ) alkyls.
  • R 1 is chosen from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, cyclohexyl, benzyl and phenyl, in particular from hydrogen, methyl, ethyl, propyl, isopropyl, cyclohexyl and benzyl.
  • R 2 is chosen from linear or branched C 3 -C 6 alkyls (in particular propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl and hexyl) and C 5 -C 8 cycloalkyls (in particular cyclopentyl). or cyclohexyl).
  • R 2 is chosen from propyl, isopropyl, cyclohexyl and benzyl.
  • R 1 and R 2 may furthermore form, together with the nitrogen atom to which they are bonded, a single hydrocarbon ring, such a hydrocarbon ring preferably having from 5 to 7 ring members and comprising in the ring 3 to 6 carbon atoms , at least one nitrogen atom and optionally one or two unsaturated double bond (s).
  • polyfunctional silane means a silane bearing on the one hand a Y function consisting of one, two or three hydroxyl groups or monovalent group (s) ( s) hydrolyzable (s) connected to a silicon atom, and secondly a function X consisting of a polythiosulfenamide group of formula (I) which is connected to the silicon atom of the Y function by the divalent linking group A.
  • polyfunctional polysiloxane means a carrier polysiloxane, in the chain and / or at the end (s) of the chain, as a function Y of at least one siloxyl unit equipped with one, two or three OH group (s) or monovalent group (s) which can be hydrolysed, and, as function X, at least one siloxyl unit equipped with a polythiosulfenamide group of formula (I).
  • the organosilicon compound of formula (I) is preferably a silane compound carrying, as function Y, one or more (maximum equal to 3) groups (OR) attached to an atom. of silicon, R representing hydrogen or a monovalent hydrocarbon group, linear or branched (especially alkyl).
  • such bifunctional organosilicon compound of formula (II) comprises a (first) "Y" function [symbolized by 1 to 3 group (s) (OR 4) is attached to the atom Silicon] connected, via the linking group A, to the polythiosulfenamide functional group of formula (I) [(second) function "X" symbolized by - S x -NR 1 R 2 ].
  • the radicals R 3 and R 4 which are identical or different, are hydrocarbon groups chosen in particular from saturated or unsaturated aliphatic hydrocarbon groups, carbocyclic, saturated, unsaturated and / or aromatic, monocyclic or polycyclic groups, and groups having a part saturated or unsaturated aliphatic hydrocarbon, and a carbocyclic moiety as defined above, preferably having 1 to 18 carbon atoms, these different groups may be substituted or unsubstituted.
  • R 3 which are identical or different if they are several, preferably represent an alkyl, a cycloalkyl or an aryl. They are more preferentially selected from the group consisting of C 1 -C 8 alkyls, C 5 -C 10 cycloalkyls (especially cyclohexyl) and phenyl. More preferably still, R 3 is selected from the group consisting of C 1 -C 6 alkyls (especially methyl, ethyl, propyl, isopropyl).
  • the radicals R 4 which are identical or different if they are several, preferably represent an alkyl, a cycloalkyl, an acyl or an aryl. They are more preferably selected from the group consisting of C 1 -C 8 alkyls, optionally halogenated and / or optionally substituted by one or more (C 2 -C 8 ) alkoxy, C 2 -C 9 acyls, optionally halogenated. and / or optionally substituted by one or more (C 2 -C 8 ) alkoxy, C 5 -C 10 cycloalkyls and C 6 -C 18 aryls.
  • R 4 is selected from the group consisting of C 1 -C 8 alkyls (especially methyl, ethyl, n-propyl, isopropyl, n-butyl, ⁇ -cloropropyl, ⁇ -chloroethyl), optionally substituted by a or more (C 2 -C 8 ) alkoxy (especially methoxy, ethoxy, propoxy, isopropoxy), C 5 -C 10 cycloalkyl and phenyl.
  • C 1 -C 8 alkyls especially methyl, ethyl, n-propyl, isopropyl, n-butyl, ⁇ -cloropropyl, ⁇ -chloroethyl
  • C 2 -C 8 alkoxy especially methoxy, ethoxy, propoxy, isopropoxy
  • C 5 -C 10 cycloalkyl and phenyl especially methoxy, ethoxy, propoxy, iso
  • R 3 and R 4 which are identical or different, are both chosen (if a ⁇ 3) from C 1 -C 4 alkyls, in particular from methyl and ethyl.
  • organosilicon compounds that may be used in the compositions of the invention, mention may be made in particular of the silanes-polythiosulfenamide of formula (II) in which the group A represents a C 1 -C 4 alkylene, in particular methylene, ethylene or propylene ( more preferably still propylene), the radicals R 3 and R 4 , which are identical or different, more preferably representing a C 1 -C 3 alkyl, in particular methyl or ethyl, and more particularly, from these compounds, the silanes-dithiosulfenamide for which x is 2.
  • the group A represents a C 1 -C 4 alkylene, in particular methylene, ethylene or propylene ( more preferably still propylene)
  • the radicals R 3 and R 4 which are identical or different, more preferably representing a C 1 -C 3 alkyl, in particular methyl or ethyl, and more particularly, from these compounds, the silanes-dithios
  • the polyfunctional coupling agents above carrying a polythiosulfenamide group, have shown very good reactivity with diene elastomers used in tire rubber compositions, and have proved sufficiently effective on their own for the coupling such elastomers and a reinforcing inorganic filler such as silica. Without this being limiting, they can advantageously constitute the only coupling agent present in the rubber compositions of the invention.
  • the amount of coupling agent used in the compositions in accordance with the invention is between 10 -7 and 10 -5 moles per m 2 of reinforcing inorganic filler. More preferably still, the amount of coupling agent is between 5 ⁇ 10 -7 and 5 ⁇ 10 -6 mol per square meter of total inorganic filler.
  • the content of coupling agent will preferably be greater than 1 phr, more preferably between 2 and 20 phr. Below the minima indicated, the effect is likely to be insufficient, whereas beyond the maximum recommended, coupling improvement is generally no longer observed, whereas the costs of the composition increase; for these different reasons, this content of coupling agent is even more preferably between 3 and 12 phr.
  • the coupling agent in order to reduce the costs of the rubber compositions, it is desirable to use the least possible, that is to say the just necessary for sufficient coupling between the diene elastomer and the reinforcing inorganic filler. Its effectiveness makes it possible, in a large number of cases, to use the coupling agent at a preferential level representing between 0.5% and 20% by weight relative to the amount of reinforcing inorganic filler; levels lower than 15%, especially less than 10%, are more particularly preferred.
  • organosilicon compound previously described could be grafted beforehand (via the "Y" function) on the reinforcing inorganic filler, the thus “pre-coupled” filler subsequently being bonded to the diene elastomer, via the free function "X".
  • organosilicon compounds as described above may be prepared according to the preferred synthetic routes indicated below (methods noted A to E).
  • a base preferably an organic base.
  • Suitable bases are, for example, N-methylmorpholine, triethylamine, tributylamine, diisopropylethylamine, dicyclohexylamine, N-methylpiperidine, pyridine, 4- (1-pyrrolidinyl) pyridine, picoline, 4- ( N, N-dimethylamino) pyridine, 2,6-di-t-butyl-4-methylpyridine, quinoline, N, N-dimethylaniline, N, N-diethylaniline, 1,8-diazabicyclo [5.4.0 ] -undec-7-ene (DBU), 1,5-diazabicyclo [4.3.0] non-5-ene (DBN) and 1,4-diazabicyclo [2.2.2] -octane (DABCO or triethylenediamine).
  • N-methylmorpholine triethylamine, tributylamine, diisopropylethylamine, dicyclo
  • the reaction is preferably carried out in a polar aprotic solvent such as an ether and, for example, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane or diethylene glycol dimethyl ether. Diethyl ether is preferred.
  • the reaction temperature is a function of the reactivity of the molecules in the presence and the strength of the base used. This temperature generally varies between -78 ° C and room temperature (15-25 ° C). Advantageously, a temperature between -78 ° C and -50 ° C is suitable. Then, it is desirable to let the medium return to room temperature.
  • the reaction is stoichiometric; in this case, the molar ratio of the amine (IX) to the disulfide halide (VIII) is chosen between 1 and 2, more preferably between 1 and 1.5.
  • the amount involved depends on the nature of the reaction product targeted.
  • the amine (IX) will be in excess in the medium reaction.
  • the molar ratio (IX) / (VIII) generally varies between 1 and 3, this ratio being generally the closest to 1, for example chosen between 1 and 1.2.
  • the substituents of the phthalimido and succinimido groups are organic substituents compatible with the reaction involved, that is to say non-reactive under the operating conditions used.
  • the bases that can be used are those defined above for Method A.
  • the reaction is carried out in an aprotic polar solvent and, preferably, an aliphatic halogenated hydrocarbon (such as methylene chloride or carbon tetrachloride) or an optionally halogenated aromatic hydrocarbon (such as benzene or an optionally halogenated toluene).
  • the solvent is CCl 4 .
  • the reaction temperature is preferably between -10 ° C and 100 ° C, more preferably between 10 ° C and 50 ° C.
  • the respective amounts of the compounds (IX) and (X) brought into contact depends on the type of organosilicon compound referred to, as in the previous case (method A).
  • the reaction temperature advantageously varies between 10 and 40 ° C, more preferably between 15 and 30 ° C, for example between 18 and 25 ° C.
  • the reaction of the compound (XII) with the compound (XI) is generally carried out in a polar aprotic solvent as defined in the case of the method B.
  • the solvent is benzene or toluene.
  • the reaction is a stoichiometric reaction.
  • the molar ratio of (XI) to (XII) will generally be between 1 and 1.5, more preferably between 1 and 1.3.
  • This variant C is especially used for the preparation of organosilicon compounds of general formula (II) in which R 1 is distinct from a hydrogen atom.
  • the compounds of formula (VIII) may be prepared by reaction of sulfur dichloride (SCI 2 ) with a suitable mercaptosilane of formula (XII) as defined above, in the presence of an organic base, and preferably in the presence of triethylamine . This reaction is carried out, for example, in an ether at a temperature of from -78 ° C. to -50 ° C.
  • Organic bases and ethers are generally as defined above.
  • Amines (IX) are commercial, or readily prepared from commercial products.
  • the compounds of formula (X) are easily prepared by reaction of a thiol of formula (XII) as defined above with the halide of formula: (XIII) JS-Hal where J and Hal are as defined above.
  • This reaction is preferably carried out in the presence of a base, in particular an organic base, at a temperature of 10 ° C. to 50 ° C., for example from 15 ° C. to 30 ° C., in particular between 18 ° C. and 25 ° C. C, in a polar aprotic solvent generally as defined in Method B.
  • a base in particular an organic base
  • the solvent is carbon tetrachloride
  • the base is triethylamine
  • the temperature is room temperature.
  • This reaction is stoichiometric; nevertheless, it is desirable to operate in the presence of a thiol defect (XII).
  • the molar ratio of the compound (XIII) to the compound (XII) is advantageously between 1 and 1.5, more preferably between 1 and 1.3.
  • the compounds of formula (XI) are easily obtained by reacting an amine (IX) with the halide of formula (XIII) in the presence of an organic base.
  • This reaction is preferably carried out in a halogenated hydrocarbon solvent (and in particular carbon tetrachloride) at a temperature generally between 10 ° C. and 50 ° C., preferably between 15 ° C. and 30 ° C., for example between 18 ° C and 25 ° C (room temperature).
  • a halogenated hydrocarbon solvent and in particular carbon tetrachloride
  • As an organic base one will opt for any of the bases defined above and, for example, for triethylamine.
  • the compounds of formula (XII) are commercially available or readily prepared from commercial compounds.
  • J and Hal are as defined above and M represents an alkali metal, preferably Na or K.
  • the commercial compound (XIV) is converted into an alkali metal salt by the action of an appropriate inorganic base, M-OH where M is an alkali metal, of the alkali metal hydroxide type in a lower C 1 -C 4 alcohol such as methanol or ethanol.
  • M is an alkali metal
  • a lower C 1 -C 4 alcohol such as methanol or ethanol.
  • This reaction generally takes place at a temperature of 15 ° C to 25 ° C.
  • the resulting salt of formula (XV) is reacted with S 2 Cl 2 to yield compound (XVI).
  • Advantageous reaction conditions for this reaction are a polar aprotic solvent of the type of a halogenated aliphatic hydrocarbon (for example CH 2 Cl 2 , CCl 4 ) and a temperature of between -20 ° C and 10 ° C.
  • Hal-Hal on the compound (XVI) leads to the compound (XIII) expected.
  • a polar aprotic solvent of aliphatic hydrocarbon or halogenated aromatic type such as chloroform, dichloromethane or chlorobenzene
  • Hal represents chlorine, in which case Hal-Hal is introduced in gaseous form into the reaction medium.
  • the rubber compositions in accordance with the invention also comprise all or part of the additives normally used in diene rubber compositions intended for the manufacture of tires, for example plasticizers, extension oils, protective agents such as anti-ozone waxes, chemical antiozonants, anti-oxidants, anti-fatigue agents, adhesion promoters, coupling activators as described for example in the applications WO00 / 05300 and WO00 / 05301 above, a crosslinking system based on either sulfur, or sulfur and / or peroxide donors and / or bismaleimides, vulcanization accelerators, vulcanization activators, etc.
  • the reinforcing inorganic filler may also be associated, if necessary, a conventional white filler with little or no reinforcing, for example particles of clay, bentonite, talc, chalk, kaolin.
  • the rubber compositions in accordance with the invention may also contain, in addition to the organosilicon compounds described above, reinforcing inorganic filler recovery agents, comprising, for example, the sole function Y, or more generally, agents for assisting the in a known manner, by improving the dispersion of the inorganic filler in the rubber matrix and by lowering the viscosity of the compositions, to improve their ability to use in the green state, these agents for example alkylalkoxysilanes (especially alkyltriethoxysilanes), polyols, polyethers (for example polyethylene glycols), primary, secondary or tertiary amines (for example trialkanol amines), hydroxylated or hydrolysable polyorganosiloxanes, for example ⁇ , ⁇ -dihydroxy-polyorganosiloxanes (especially ⁇ , ⁇ -dihydroxy-polydimethylsiloxanes).
  • reinforcing inorganic filler recovery agents comprising, for
  • compositions are manufactured in appropriate mixers, using two successive preparation phases well known to those skilled in the art: a first phase of work or thermomechanical mixing (sometimes called a "non-productive" phase) at high temperature, up to a maximum temperature (denoted T max ) of between 110 ° C. and 190 ° C., preferably between 130 ° C.
  • T max maximum temperature
  • a second mechanical working phase (sometimes referred to as a "productive" phase) at lower temperature, typically below 110 ° C, for example between 60 ° C and 100 ° C, finishing phase during which the crosslinking or vulcanization system is incorporated; such phases have been described for example in the applications EP 501 227 , EP 735 088 , EP 810 258 , EP 881 252 , WO00 / 05300 or WO00 / 05301 above.
  • the manufacturing method according to the invention is characterized in that at least the reinforcing inorganic filler and the organosilicon compound are incorporated by kneading with the diene elastomer, during the first so-called non-productive phase, that is to say that is, introducing into the mixer and thermomechanically kneading, in one or more steps, at least these various basic constituents until a maximum temperature of between 110 ° C. and 190 ° C. is reached, preferably between 130 ° C and 180 ° C.
  • the first (non-productive) phase is carried out in a single thermomechanical step during which, in a suitable mixer such as a conventional internal mixer, all the necessary basic constituents are first introduced. (Diene elastomer, reinforcing inorganic filler and organosilicon compound), then in a second step, for example after one to two minutes of mixing, any additional coating or processing agents and other various additives, with the exception of the system vulcanization; when the bulk density of the reinforcing inorganic filler is low (general case of silicas), it may be advantageous to split its introduction into two or more parts.
  • a suitable mixer such as a conventional internal mixer
  • thermomechanical work step may be added to this internal mixer, after the mixture has fallen and intermediate cooling (cooling temperature preferably below 100 ° C.), in order to subject the compositions to a complementary thermomechanical treatment, in particular to improve still further, the dispersion in the elastomeric matrix of the reinforcing inorganic filler and its coupling agent.
  • the total mixing time, in this non-productive phase, is preferably between 2 and 10 minutes.
  • the vulcanization system is then incorporated at low temperature, generally in an external mixer such as a roll mill; the whole is then mixed (productive phase) for a few minutes, for example between 5 and 15 minutes.
  • the final composition thus obtained is then calendered, for example in the form of a sheet, a plate or extruded, for example to form a rubber profile used for the manufacture of semi-finished products such as treads, tablecloths crowns, flanks, carcass reinforcement plies, heels, protectors, inner tubes or tubeless tire liner.
  • the vulcanization (or cooking) is conducted in a known manner at a temperature generally between 130 ° C and 200 ° C, preferably under pressure, for a sufficient time which may vary for example between 5 and 90 min depending in particular on the temperature cooking, the vulcanization system adopted, the vulcanization kinetics of the composition in question or the size of the tire.
  • the vulcanization system itself is preferably based on sulfur and a primary vulcanization accelerator, in particular a sulfenamide type accelerator.
  • a primary vulcanization accelerator in particular a sulfenamide type accelerator.
  • various known secondary accelerators or vulcanization activators such as zinc oxide, stearic acid, guanidine derivatives (especially diphenylguanidine), etc.
  • Sulfur is used at a preferential rate of between 0.5 and 10 phr, more preferably between 0.5 and 5.0 phr, for example between 0.5 and 3.0 phr, when the invention is applied to a strip. of tire rolling.
  • the primary vulcanization accelerator is used at a preferential rate of between 0.5 and 10 phr, more preferably between 0.5 and 5.0 phr, in particular when the invention is applied to a tire tread.
  • the invention relates to the rubber compositions described above both in the so-called “raw” state (ie, before firing) and in the so-called “cooked” or vulcanized state (ie, after crosslinking or vulcanization).
  • the compositions in accordance with the invention can be used alone or in a blend (ie, in a mixture) with any other rubber composition that can be used for the manufacture of tires.
  • the coupling agents that can be used preferentially in the compositions of the invention are silanes-dithiosulfenamide, more preferentially alkoxysilanes corresponding to one of the formulas (III) to (VII), the modes of synthesis of which are described below, As non-limiting examples.
  • the boiling points (Eb pressure ) are given in millibars (mbar).
  • the 250 MHz spectra of the proton ( 1 H NMR) and carbon ( 13 C NMR) are recorded on a BRUCKER AC 250 spectrometer.
  • the chemical shifts ( ⁇ c and ⁇ h) are expressed in parts per million (ppm) relative to deuterochloroform ( CDCl 3 ).
  • the coupling constants denoted J are expressed in Hz.
  • the following abbreviations are used: s, singlet; sl, broad singlet ; d, doublet ; t, triplet; q, quadruplet ; m, multiplet.
  • N- (3-trimethoxysilylpropyldisulfanyl) -bis (isopropyl) amine also called di (isopropyl) trimethoxysilylpropyldithio-sulfenamide, is synthesized in three steps.
  • the sulphide obtained in the preceding step (50 mmol) is dissolved in 250 ml of benzene.
  • 3-mercaptopropyltrimethoxysilane (45 mmol) diluted in a minimum of benzene is added in one go. It is stirred at room temperature for 48 hours. Precipitated phthalimide and excess sulfide are filtered and the solvent is evaporated under reduced pressure.
  • reaction medium is stirred at this temperature for one hour and then a mixture of cyclohexylmethylamine (110 mmol) and triethylamine (100 mmol, 10.2 g) in 100 ml of anhydrous diethyl ether is added dropwise over one hour.
  • the reaction medium is allowed to return to ambient temperature and then the triethylamine hydrochloride is filtered and concentrated under reduced pressure. Distillation under reduced pressure makes it possible to remove traces of unreacted reagents.
  • the mixture is stirred for 12 hours while allowing the reaction medium to return to room temperature, and then the precipitated triethylamine hydrochloride is filtered, the precipitate is washed with anhydrous diethyl ether and concentrated under reduced pressure. Distillation under reduced pressure makes it possible to remove the excess of triethylamine and cyclohexylamine, and thus to isolate 30 g of the desired compound.
  • N- (3-ethoxydimethylsilylpropyldisulfanyl) -bis (isopropyl) amine or di (isopropyl) ethoxydimethylsilylpropyldithio-sulfenamide is synthesized in four steps.
  • N- (N ', N'-bis (isopropyl) aminosulfanyl) phthalimide (30.51 g, 109.7 mmol) is dissolved in dichloromethane (600 ml). ). 3-mercaptopropylethoxydimethylsilane (18.02 g, 101 mmol) is added at ambient temperature at a flow rate of 5 ml / min. It is stirred at room temperature for 20 hours. The phthalimide which precipitated is filtered and the solvent is evaporated off under reduced pressure. The paste obtained is taken up in toluene. The phthalimide which precipitated and the excess sulphide are filtered and then evaporated under reduced pressure.
  • the diene elastomer (or the mixture of diene elastomers) is introduced into an internal mixer, filled to 70% and whose initial tank temperature is approximately 60 ° C. , if necessary), the reinforcing filler, the coupling agent, then, after one to two minutes of mixing, the various other ingredients with the exception of the vulcanization system.
  • Thermomechanical work (non-productive phase) is then carried out in two stages (total mixing time equal to about 7 minutes), until a maximum "falling" temperature of approximately 165 ° C. is reached.
  • the mixture thus obtained is recovered, cooled and the vulcanization system (sulfur and sulfenamide accelerator) is added to an external mixer (homo-finisher) at 30 ° C., mixing the whole (productive phase) for 3 to 4 minutes. .
  • vulcanization system sulfur and sulfenamide accelerator
  • compositions thus obtained are then calendered either in the form of plates (thickness of 2 to 3 mm) or thin sheets of rubber for the measurement of their physical or mechanical properties, or in the form of profiles that can be used directly, after cutting and / or or assembly to the desired dimensions, for example as semi-finished products for tires, in particular as treads of tires.
  • the diene elastomer is an SBR / BR blend and the reinforcing inorganic filler (HDS silica) is used at a preferential rate within a range of 50 to 120 phr.
  • TESPT is bis (3-triethoxysilylpropyl) tetrasulfide of formula [(C 2 H 5 O) 3 Si (CH 2 ) 3 S 2 ] 2 ; it is marketed for example by the company Degussa under the name Si69 (or X50S when it is supported at 50% by weight on carbon black), or by the company Witco under the name Silquest A1289 (in both cases, commercial polysulfide mixture S x with a mean value for x which is close to 4).
  • TESPT The developed formula of TESPT is:
  • the level of coupling agent is in both cases less than 10 phr, which represents less than 15% by weight relative to the amount of reinforcing inorganic filler.
  • Tables 1 and 2 give the formulation of the various compositions (Table 1 - rate of the different products expressed in phr), their properties before and after curing (40 min at 150 ° C.).
  • the appended figure reproduces the modulus curves (in MPa) as a function of the elongation (in%), these curves being denoted C1 and C2 and respectively corresponding to compositions Nos. 1 and 2.
  • the composition of the invention (curve C2), compared to the control composition (curve C1), reveals a higher level of reinforcement (modulus) regardless of the level of elongation, in particular at high deformation (elongations of 100% and more); for such a range of elongations, this behavior clearly illustrates a better quality of the bond or coupling between the reinforcing inorganic filler and the diene elastomer, indicating a very good ability of the composition of the invention to withstand wear.
  • silane of formula (XIX) does not fulfill the conditions required by the invention, because of the nature of its radicals R 1 and R 2 (ethyl instead of C 3 -C 8 alkyl).
  • silane of formula (XIX) has in particular been described in the patent US-A-4,292,234 and exemplified as a coupling agent in silica-reinforced elastomeric compositions (see Table IV).
  • the three coupling agents tested are used at an isomolar silicon level, that is to say that the same number of moles of functions is used regardless of the composition.
  • the level of coupling agent is less than 10 phr (ie less than 15% by weight relative to the amount of silica).
  • Tables 3 and 4 give the formulation of the various compositions (Table 3 - rates of the various products expressed in phr), their properties before and after curing (40 min at 150 ° C.), as well as the rheometric properties at 150 ° C.
  • the coupling agent selected for the compositions according to the invention gives the latter high reinforcing properties, excellent processing properties in the green state thanks to reduced plasticity, very good to vulcanization, thus revealing an overall efficiency higher than that of TESPT, a reference coupling agent in diene rubber compositions reinforced with an inorganic filler such as a reinforcing silica, as with that of the dithiosulfenamide silane described in document US-A-4,292,234 supra.
  • the invention finds particularly advantageous applications in rubber compositions for the manufacture of tire treads having both low rolling resistance and high wear resistance, particularly when these treads are intended tires for passenger cars, motorcycles or industrial vehicles of the heavy truck type.

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EP02796682A 2001-12-20 2002-12-19 Composition de caoutchouc pour pneumatique comportant un agent de couplage a fonction polythiosulfenamide Expired - Lifetime EP1474475B1 (fr)

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US7367369B2 (en) * 2004-09-23 2008-05-06 The Goodyear Tire & Rubber Company Aircraft tire
DE102006004062A1 (de) * 2006-01-28 2007-08-09 Degussa Gmbh Kautschukmischungen
RU2009135631A (ru) * 2007-03-27 2011-03-27 Бриджстоун Корпорейшн (Jp) Способ получения резиновой смеси для беговой дорожки протектора
WO2009104766A1 (ja) * 2008-02-22 2009-08-27 株式会社ブリヂストン 有機ケイ素化合物、並びにそれを用いたゴム組成物、タイヤ、プライマー組成物、塗料組成物及び接着剤
FR2935980B1 (fr) * 2008-09-18 2010-12-03 Soc Tech Michelin Flanc pour pneumatique.
JP5513010B2 (ja) * 2009-05-20 2014-06-04 株式会社ブリヂストン 有機ケイ素化合物、並びにそれを用いたゴム組成物、タイヤ、プライマー組成物、塗料組成物及び接着剤
CN102395473B (zh) * 2009-04-29 2014-12-17 米其林集团总公司 用于重型车辆轮胎的胎面
FR2947552B1 (fr) * 2009-05-20 2011-08-26 Michelin Soc Tech Agent de couplage organosilane
JP5653162B2 (ja) * 2010-10-18 2015-01-14 株式会社ブリヂストン 有機ケイ素化合物、並びにそれを用いたゴム組成物、タイヤ、プライマー組成物、塗料組成物及び接着剤
DE102011055966B4 (de) * 2011-12-02 2024-05-16 Continental Reifen Deutschland Gmbh Kautschukmischung und deren Verwendung
JP6023579B2 (ja) * 2012-12-19 2016-11-09 株式会社ブリヂストン ゴム組成物の製造方法、ゴム組成物及びタイヤ
CN105315525A (zh) * 2015-12-09 2016-02-10 山东玲珑轮胎股份有限公司 高抗湿滑和低滚动阻力的轮胎胎面胶料及其制法和应用

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US4292234A (en) * 1979-03-30 1981-09-29 Phillips Petroleum Co. Silane reinforcing promoters in reinforcement of silica-filled rubbers
CA1222588A (en) * 1981-09-10 1987-06-02 Jennings P. Blackwell Glass-filled polyarylene sulfide compositions containing organosilanes
CA2261252A1 (en) * 1998-02-26 1999-08-26 Friedrich Visel Asymmetrical siloxy compounds
US6084014A (en) * 1998-03-02 2000-07-04 The Goodyear Tire & Rubber Company Asymmetrical siloxy compounds
EP1063259A1 (de) * 1999-06-26 2000-12-27 Bayer Ag Mikrogelhaltige Kautschukcompounds mit schwefelhaltigen Organosiliciumverbindungen
EP1204702B1 (fr) * 2000-05-26 2012-04-25 Société de Technologie Michelin Composition de caoutchouc utilisable comme bande de roulement de pneumatique

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EP1474475A1 (fr) 2004-11-10
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